Facile patterning of reduced graphene oxide film into microelectrode array for highly sensitive sensing.

In this study, we develop a new technique to fabricate a reduced graphene oxide (rGO)-based microelectrode array (MEA) with low-cost soft lithography. To prepare patterned rGO, a polydimethylsiloxane (PDMS) mold with an array of microwells on its surface is fabricated using soft lithography, and GO is assembled on an indium tin oxide (ITO) electrode with a layer-by-layer method. The rGO pattern is formed by closely contacting the assembled GO film onto the ITO electrode with the PDMS mold filled with hydrazine solution in the microwells to selectively reduce the localized GO into the rGO. The MEA with patterned rGO as the microelectrode is characterized with Kelvin probe force microscopy (KFM), atomic force microscopy (AFM), and cyclic voltammetry (CV) with ferricyanide in aqueous solution as the redox probe. The KFM and AFM results demonstrate that each rGO pattern prepared under the present conditions is 3 μm in diameter, which is close to that of the PDMS mold we use. The CV results show that the rGO patterned onto the ITO exhibits a sigmoid-shaped voltammogram up to 200 mVs(-1) with a microampere level current response, suggesting that the rGO-based electrode fabricated with soft lithography behalves like a MEA. To demonstrate the potential electroanalytical application of the rGO-based MEA, prussian blue (PB) is electrodeposited onto the rGO-based MEA to form the PB/rGO-based MEA. Electrochemical studies on the formed PB/rGO-based MEA reveal that MEA shows a lower detection limit and a larger current density for the detection of H(2)O(2), as compared with the macroscopic rGO electrode. The method demonstrated here provides a simple and low-cost strategy for the fabrication of graphene-based MEA that are useful for electroanalytical applications.

[1]  Ling Xiang,et al.  In situ cationic ring-opening polymerization and quaternization reactions to confine ferricyanide onto carbon nanotubes: a general approach to development of integrative nanostructured electrochemical biosensors. , 2008, Analytical chemistry.

[2]  Xi Zhang,et al.  Unconventional layer-by-layer assembly of graphene multilayer films for enzyme-based glucose and maltose biosensing. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[3]  L. Liu,et al.  Fabrication of Graphene Nanodisk Arrays Using Nanosphere Lithography , 2008 .

[4]  Ying Wang,et al.  Preparation, Structure, and Electrochemical Properties of Reduced Graphene Sheet Films , 2009 .

[5]  Yang Yang,et al.  High-throughput solution processing of large-scale graphene. , 2009, Nature nanotechnology.

[6]  S. Stankovich,et al.  Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide , 2007 .

[7]  Itaru Honma,et al.  Enhanced electrocatalytic activity of Pt subnanoclusters on graphene nanosheet surface. , 2009, Nano letters.

[8]  F Ricci,et al.  Sensor and biosensor preparation, optimisation and applications of Prussian Blue modified electrodes. , 2005, Biosensors & bioelectronics.

[9]  Yuehe Lin,et al.  Glucose Biosensors Based on Carbon Nanotube Nanoelectrode Ensembles , 2004 .

[10]  Kwang S. Kim,et al.  Large-scale pattern growth of graphene films for stretchable transparent electrodes , 2009, Nature.

[11]  Kian Ping Loh,et al.  Microstructuring of Graphene Oxide Nanosheets Using Direct Laser Writing , 2010, Advanced materials.

[12]  G. Wallace,et al.  Processable aqueous dispersions of graphene nanosheets. , 2008, Nature nanotechnology.

[13]  Dan Li,et al.  Comparative studies on electrochemical activity of graphene nanosheets and carbon nanotubes , 2009 .

[14]  J. Savéant,et al.  Charge transfer at partially blocked surfaces , 1983 .

[15]  A. Stemmer,et al.  Permanent pattern-resolved adjustment of the surface potential of graphene-like carbon through chemical functionalization. , 2009, Angewandte Chemie.

[16]  X. Xia,et al.  Multilayer assembly of Prussian blue nanoclusters and enzyme-immobilized poly(toluidine blue) films and its application in glucose biosensor construction. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[17]  J. Anzai,et al.  Layer-by-layer construction of enzyme multilayers on an electrode for the preparation of glucose and lactate sensors: elimination of ascorbate interference by means of an ascorbate oxidase multilayer. , 1998, Analytical chemistry.

[18]  G. Whitesides,et al.  Fabrication of three‐dimensional micro‐structures: Microtransfer molding , 1996 .

[19]  Jingjing Xu,et al.  Hierarchical nanocomposites of polyaniline nanowire arrays on graphene oxide sheets with synergistic effect for energy storage. , 2010, ACS nano.

[20]  Peng Chen,et al.  Centimeter-long and large-scale micropatterns of reduced graphene oxide films: fabrication and sensing applications. , 2010, ACS nano.

[21]  D. Astruc,et al.  Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. , 2004, Chemical reviews.

[22]  N. Adachi,et al.  Measurement of the extracellular H2O2 in the brain by microdialysis. , 1998, Brain research. Brain research protocols.

[23]  S. Dong,et al.  Electrochemical sensing and biosensing platform based on chemically reduced graphene oxide. , 2009, Analytical chemistry.

[24]  Kian Ping Loh,et al.  Hydrothermal Dehydration for the “Green” Reduction of Exfoliated Graphene Oxide to Graphene and Demonstration of Tunable Optical Limiting Properties , 2009 .

[25]  Mianqi Xue,et al.  Processing of graphene for electrochemical application: noncovalently functionalize graphene sheets with water-soluble electroactive methylene green. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[26]  Norio Teramae,et al.  2-Aminopurine-modified abasic-site-containing duplex DNA for highly selective detection of theophylline. , 2009, Journal of the American Chemical Society.

[27]  G. Whitesides,et al.  New approaches to nanofabrication: molding, printing, and other techniques. , 2005, Chemical reviews.

[28]  John A Rogers,et al.  Soft lithography using acryloxy perfluoropolyether composite stamps. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[29]  Yanlian Yang,et al.  Processing Matters: In situ Fabrication of Conducting Polymer Microsensors Enables Ultralow‐Limit Gas Detection , 2008 .

[30]  K. Novoselov,et al.  Detection of individual gas molecules adsorbed on graphene. , 2006, Nature materials.

[31]  Filip Braet,et al.  Carbon nanomaterials in biosensors: should you use nanotubes or graphene? , 2010, Angewandte Chemie.

[32]  R. R. Moore,et al.  Basal plane pyrolytic graphite modified electrodes: comparison of carbon nanotubes and graphite powder as electrocatalysts. , 2004, Analytical chemistry.

[33]  Shana O Kelley,et al.  Nanostructuring of patterned microelectrodes to enhance the sensitivity of electrochemical nucleic acids detection. , 2009, Angewandte Chemie.

[34]  S. Kounaves,et al.  Microfabricated Ultramicroelectrode Arrays: Developments, Advances, and Applications in Environmental Analysis , 2000 .

[35]  Shana O Kelley,et al.  Ultrasensitive electrocatalytic DNA detection at two- and three-dimensional nanoelectrodes. , 2004, Journal of the American Chemical Society.

[36]  R. Waltman,et al.  X-ray photoelectron spectroscopic studies on organic photoconductors: evaluation of atomic charges on chlorodiane blue and p-(diethylamino)benzaldehyde diphenylhydrazone , 1993 .

[37]  K. Ino,et al.  Electrochemical gene-function analysis for single cells with addressable microelectrode/microwell arrays. , 2009, Angewandte Chemie.

[38]  M. Meyyappan,et al.  Carbon Nanotube Nanoelectrode Array for Ultrasensitive DNA Detection , 2003 .

[39]  K. Loh,et al.  A graphene oxide-organic dye ionic complex with DNA-sensing and optical-limiting properties. , 2010, Angewandte Chemie.

[40]  Lei Su,et al.  Electrochemistry and Electroanalytical Applications of Carbon Nanotubes: A Review , 2005, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[41]  Trevor J. Davies,et al.  The cyclic and linear sweep voltammetry of regular and random arrays of microdisc electrodes: Theory , 2005 .

[42]  Itamar Willner,et al.  Biomolecule-functionalized carbon nanotubes: applications in nanobioelectronics. , 2004, Chemphyschem : a European journal of chemical physics and physical chemistry.

[43]  G. Rechnitz,et al.  Toxin detection using a tyrosinase-coupled oxygen electrode. , 1993, Analytical chemistry.

[44]  Continuous on-line measurement of cerebral hydrogen peroxide using enzyme-modified ring-disk plastic carbon film electrode. , 2002, Analytical chemistry.

[45]  Lo Gorton,et al.  On the mechanism of H2O2 reduction at Prussian Blue modified electrodes , 1999 .

[46]  Kingo Itaya,et al.  Catalysis of the reduction of molecular oxygen to water at Prussian blue modified electrodes , 1984 .

[47]  P. Sheehan,et al.  The assembly of single-layer graphene oxide and graphene using molecular templates. , 2008, Nano letters.

[48]  T. Ohsaka,et al.  A novel electrochemical strategy for developing alkaline air electrodes by a combined use of dual functional catalysts. , 2003, Chemical communications.